Process Intensification - Climbing the S-curve · Process Intensification • Currently a...
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Process Intensification -
Climbing the S-curve
Y.C. van Delft
November 2014
ECN-L--15-068
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www.ecn.nl
Process Intensification Climbing the S-curve
Y.C. van Delft PIN-NL Autumn Session 2014 Amersfoort, 19 November 2014
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ECN: A rich and evolving history
~600 employees
~500 reports in 2011 ~270 conferences in 2011
~20 patents a year
~5 licenses a year
We are in our 58th year of pushing technology boundaries
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Position
fundamental research
industrial development
• independent • connecting partners
Industrial partners Universities
applied research
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Driver for ECN
4
• Primary and final energy consumption of the Dutch chemical & refining industry (data 2000)
• Chemical & refining = 30% of primary energy (including feedstock)
Electricity 42 PJ
Conversion loss Electricity 30 PJ
Oil
Natural gas
Other
837
PJ 494 PJ
253 PJ
50 PJ
Feedstock 379 PJ
Fina
l ene
rget
ic u
se
373
PJ
Heat 331 PJ
Total NL= 3051 Total NL= 2518
Driver: increasing the efficiency of the chemical and refining industry
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Energy loss in the Dutch chemical industry
• Extensive database of Dutch chemical processes
• Covers to 100+ of processes (energy use) • Searchable on specific aspects • Valuable tool for analysis of potential of
technologies
5
NH3+MeOH 21%
Others (exo) 11%
Others (endo)
5%
Oxidation 30%
Cracking 19%
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Process and technology selection
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NH3+MeOH 21%
Others (exo) 11%
Others (endo) 5%
Oxidation 30%
Cracking 19%
Energy use in the Dutch chemical industry (2005)
G. Agricola, De Re Metallica, 1556
Chemical Process Industry, 2013
Drastic improvement of efficiency needs process innovation => Process Intensification!
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Process and technology selection
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NH3+MeOH 21%
Others (exo) 11%
Others (endo) 5%
Oxidation 30%
Cracking 19%
Energy use in the Dutch chemical industry (2005)
Pervaporation membranes Industrial heat pumps Oxidation in a Taylor flow reactor Sorption enhanced reactions Heat integrated distillation Membrane reactor for hydrogen production Membrane esterification
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PI domains
• Focus ECN: – PI technologies combining
known functions – From lab to pilot – From particles/thin films
to processing units
Synergy
Energy
Structure
Time
(based on: Andrzej Stankiewicz, TU Delft
HIDiC H2MR
TFR SER ME
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PI technology: from lab to pilot
9
Operability
Lab scale testing
Equipment design
Bench-scale
Process design
Piloting
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Process Intensification: role of scales
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Length [m] 10 -10 10 -8 10 -6 10 -4 10 -2 10 0 10 2
Molecular processes
Catalysts/Reaction processes, particles, thin films Processing units
Chemical plant / site
Hydrodynamics & transport processes, single & multi phase systems
“from the molecule to the plant” (based on: Andrzej Stankiewicz, TU Delft
10 4
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PI at ECN
H2MR: Pd-membranes
TRL
HIDiC-PP
ME
SEWGS Heat Transfer
Equilibrium Limitation
Mass Transfer
HIDiC
SER
H2MR
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Process Intensification development lines
• Separation enhanced reactions – Membrane reformer (hydrogen separation) – SEWGS (CO2 separation) – Membrane esterifications
• Direct selective addition of reactants to a reaction
• Structured reactors for oxidations • Heat integrated distillation
• Process and system studies – In cooperation with equipment manufacturers and
end-users 12
Catalyst technology
Membrane technology
Sorption technology
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Membrane R&D at ECN • Different membranes and their development status:
– Dense metal-based membranes: – H2-separation (HySep)
– Hybrid nano-porous membranes: – Pervaporation (HybSi: Separation of water/methanol from solvents) – CO2- and H2O-separation
Nanoporous membranes: Gas separation
Membrane Reactor: Pd-membranes
Hybpon: nanofiltration liquids Hybrid nanoporous membranes
HybSi: Hybrid nano-porous membranes
Hysep: Pd-membranes
TRL
Development Time
Membrane Reactor: Esterifications
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Sorbent R&D at ECN • Different sorbents and their development status:
– Hydrotalcites for HT separations and reactions: – CO2, H2S and H2O separations – Reforming, Refineries and CCS
– Low temperature Sorbents: – CO2, H2S and H2O separations – Biogas and Natural gas
NH3: In situ
SEWGS: NG-based
SEWGS: Sour Conditions
ERASE: HT CO2/H2S
TRL
Development Time
CO2 /H2S: Low Temp
ERASE: HT H2O
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HIDiC R&D at ECN • Different concepts and their development status:
– Application: – Separation of close boiling liquids (P/P, EB/Styrene)
– Concentric tray HIDiC (TUD, JP) – Structured HIDiC (ECN):
– Plate fin – Plate packing
S-HIDiC
VRC
CT-HIDiC TRL
plate-fin
plate-packing
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Separation Enhanced Reactions: What problem are we trying to solve?
• Many chemical reactions are thermodynamically limited in conversion
• Consequences: – Multiple passes
– i.e. large recycles – Multiple reactors
– Heat management – Need to separate products from reactants
– Expensive distillation / cold box technology
Separation-enhanced reaction/catalysis lessens impact of thermodynamic limitation
Ammonia – Methanation – Water Gas Shift – Reverse Water-Gas Shift – Methanol – Steam Reforming – Condensation Reactions
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Example: Membrane Esterification
• Membrane esterification – If a higher production yield is required or if separation is difficult e.g. 5 azeotropes in
acetal production – In-situ removal of water during reaction can lead to much higher conversions than
normally obtainable at thermodynamic equilibrium
In situ removal of water
R-C-OH + HO-R’ ↔ R-C-O-R’ + H2O
O ||
O ||
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Membrane Esterification
In situ removal of water R-C-OH + HO-R’ ↔ R-C-O-R’ + H2O
O ||
O ||
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Membrane Esterification
cold trap
permeate (e.g. H 2 O)
reactor
vacuum pump
membrane
product (+ heavies)
raw materials
entrainer (e.g. xylene)
reactor
condenser
column
product (+ heavies)
raw materials
• Higher productivity
• Reduced energy use
• Better product quality
• Less feedstock use
Previous studies on esterification with membranes, have shown 30% productivity increase, 40% lower OPEX and 25% lower CAPEX are possible in industrial processes
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Status of H2MR: From powder to demonstration
Ceramic powders Catalyst powders Metal-organic precursors
Ceramic processing Deposition techniques Shaping processes
Membranes Catalyst
Reactor design System studies Techno-economic analysis
Lab scale demonstration units Pilot reactors
On site pilot to full scale plant
Manufacturing facility from lab to pilot scale Reactor demonstration from lab to pilot scale
Technology Scale-up After-care Licensing
Assistance in technology scale-up
Manufacturing industry
Reactor constructors, EPCM’s
End-user
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Status of SEWGS: From powder to demonstration
Ceramics Catalysts Sorbents
Ceramic processing Deposition techniques Shaping processes
High Temperature Sorbents
Reactor design System studies Techno-economic analysis
Lab scale demonstration units - Pilot reactors
On site pilot to full scale plant
Manufacturing facility from lab to pilot scale Reactor demonstration from lab to pilot scale
Technology Scale-up After-care Licensing
Assistance in technology scale-up
Manufacturing industry
Reactor constructors, EPCM’s
End-user
Impregnation Precipitation-Deposition Sol-Gel
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VRC
HybSi
S-SEWGS
Hysep
SEWGS CT-HIDiC
S-HIDiC
ERASE
MR
Hybpon
ERASE
In-situ Nano-porous Membranes
Climbing the S-Curve
PB-CLC Heat Integration Sorbents Membranes LT Adsorbents
Technology Readiness Level
Development Time
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From the molecules to plants…
Development of catalysts, membranes and sorbents
0
10
20
3500 3000 2500
Kubelka-Munk / Wavenumber (cm-1)
O-H vibrations
-Si-OH-Al-Al-OH
Si-OH
GuRECN ECN
SO20
10
20
3500 3000 2500
Kubelka-Munk / Wavenumber (cm-1)
O-H vibrations
-Si-OH-Al-Al-OH
Si-OH
GuRECN ECN
SO20
10
20
3500 3000 2500
Kubelka-Munk / Wavenumber (cm-1)
O-H vibrations
-Si-OH-Al-Al-OH
Si-OH
GuRECN ECN
SO2
Characterisation of catalysts, membranes and sorbents
Testing of of catalysts, membranes and sorbents
Process development,
reactor evaluation
Reactor Design
Process design, Systems analysis
Sustainable Process Technology
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ECN’s unique view on Process Intensification
• Currently a relatively large group at ECN with knowledge and understanding of separation & conversion with adsorbents, membranes and structured devices – Unique equipment available for study of separations & separation-enhanced reactions – Running start on developing new processes – Benefit from the large number of materials tested in previous projects – Solutions/approaches for Close boiling liquids, Ammonia, Methanation, Water Gas
Shift, Reverse Water Gas Shift, Methanol, Steam Reforming, Condensation Reactions
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Congratulations and Welcome at ECN on April 14th, 2015
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8
ECN
Westerduinweg 3 P.O. Box 1
1755 LE Petten 1755 LG Petten
The Netherlands The Netherlands
T +31 88 515 4949
F +31 88 515 8338
info@ ecn.nl
www.ecn.nl